Fluid oscillator analyzer and method



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Qsept 2\ J l v ,FLUID OSCILLA'IOR A NALYZEP. AND METHOD meaning. 12,1963 CROSS REFERENCE @sheets-sheet 1 moroni@ mOP/JAZUmO Sept 2 0 1956.. M. K. TESTERMAN ETAL 3,273,377 FLUID OSCILLATORANALYZER AND METHOD l I `Filed Aug. 12.. 1963 2 sheets-sheet z I chromatography.

" opposite outlet passages.

. A y 3,273,377 FLUID SCILLATOR A.\'.\LYZER AND METHOD Maurice K. Testcrman and Paul C. McLeod, Jr., Little Rock, Ark., assignors to Phillips Petroleum Company, a corporation of Delaware Filed Aug. 12, 1963, Ser. No. 391,418

Claims. (Cl. 'I3- 231) *i United 'Staes Parent 'O This invention relates to uid oscillators. In another t aspect it relates to the arr-'lysis of fluid streams to determine changes in composition thereof. In still another aspect it relates to detectors for use in chromatographic analyzers.

ln various industrial and laboratory procedures there is al need to detect changes in composition of fiuid mix- `turcs. -One such need occurs in making analyses by l In aV conventional chromatographic analyzer, a tiuid sample to he analyzed is injected into a column which contains a packing material that selectively retard'spassage of the individual constituents of the* Y fluid sample. A carrier gas is directed through the column to elute the constituents of the fluid sample in sequence. The presence of the individual sample constituentskin the column cflluent normally is detected by comparing the thermal conductivity of the column efiiuent with the 'i thermal'concuctivity of a reference gas, such as the carrier gas. While these thermal conductivity detectors are Y satisfactory for many analyses. detectors having greater f sensitivity are desirable for some applications.

ln accordance with this invention, a novel gas analyzer .is provided which is in the form of a tiuid oscillator. A

tiuid stream to be detected is directed through an orifice and then divided into two streams which ow through respective outlet passages. A portion of each of the resulting outlet'streams is removed and returned to the main stream at the outlet of the orifice. These returned streams impinge upon the orifice effluent in opposition to one another and tend to divert the main stream into I v In this manner, the stream directed through the orifice tends to oscillate back and forth' at a frequency which is a function of the'molecular weight of thel fluid stream.' If the molecular weightof this stream should increase, 'there is greater inertia which tends' to prevent the stream from shifting as rapidly as 'before.

positioning a pressure sensitive device in either of the The resulting `oscillations can be detected by outlet streams. When the apparatus of this invention is employed in a chromatographic analyzer, one detector receives the column efiluent and a second detector receives a sample of reference gas. The frequencies of oscillation of the two detectors can be compared so that any difer- .1r ence is indicative of sample fluid in the-column efliuent.

Accordingly, it is an object of this invention to providek v va novel fluid oscillator.

Another object is to provide a method of and apparatus l i for detectingchangesk in composition of fluid streams.

ZA further object is to provide an improved detection system for use in chromatographic analyzers.

Other objects, advantages and features of the invention should become apparent from the following detailed description, taken in conjunction withthe accompanying drawing in which:

FIGURE l is a schematic representation of a chromatographic analyzer having the detection system of this invention incorporated therein.

FIGURE 2 illustrates the configuration of an embodiment of the tiuidoscillator of this invention.

FIGURE 3 is a cross-sectional view, taken along line 3-3 of FIGURE 2, of the assembled uid oscillator of this invention.

Referring now to the drawing in detail and to FIGURE 3,273,377 Patented Sept. 20, 1956 is associated with conduit 12 to maintain the rate of flow therethrough at a preselected constant rate. A sample mixture to be analyzed introduced intoV valve I3 by means ofa conduit ,15. Valve 13 can he of the type which periodically injects a preselected amount of this sample into the carrier gas. The eflluent from valve'13 is directed to the inlet of column I9 by means of a conduit 16. The column eluent is directed by means of a conduit 17 to the inlet of a first fluid oscillator 18. lConduit 19, which has a flow controller therein, communicatesy with the inlet of a second fluid oscillator 20. i

As will be described hereinafter in detail, loscillators I8 and 20 establish vibrations at frequencies which are functions of the composition of the gas streams introduced '24 and 25. The output signals of the two microphones are applied to a mixer circuit 26 which establishes an output signal that is representative of the difference hetween the frequencies of the vibrations established by the two oscillators. The output of mixer 26 is appliedy to av detector 27 .which is capable of measuring the resulting beat frequency. The miner can include a lowpass filter toA block the relatively high frequency signals of the oscillators and pass only the relatively lou.t beat frequency.

Prior to the introduction of a fluid lsample into the system, carrier gas flows through column 10 to oscillator 18vand directly to oscillator 20. Flow controllers iiand 21 are adjusted so that oscillators 18 and 20 establish output signals of the same frequency. .A fluid sample to be analyzed is injected into the system by operation of valve 13. The etiluent from column 19 thereafter includes in sequence the individual constituents of the sample mixture. When these constituents enter oscillator 18, the frequency of the vibrations of the oscillator is changed so that an output beat frequency signal appears at detector 27. 3 Y

An embodiment of the fluid oscillator of this invention is illustrated schematically in FIGURES 2 and 3. As shown in FIGURE 3, two solid plates. 30 and 31 are separated by a relatively thin plate 32. The three plates are secured together by suitable bolts 33. The uid sample to be analyzed is introduced through a passage 34 in plate 31. Plate 32 is provided witii :i cavity which has the configuration illustrated in FIGURE 2. An inlet. chamber 35 is formed in plate 32 adjacent inlet passage 34. An orifice 36 is formed at thc outlet of chamber 35. The gas stream which is introduced through passage 34 tiows through orifice 36 and then divides so that approximately one half of the flow enters each of divergng passages 37 and 38. A portion of the gas stream which enters passage 37 flows through an outlet passage 39. and the remain/.ler flows through a return passage which extends to a point immediately downstream of orifice 36. In a similar fashion. the gas which enters passage 38 flows in part through an outlet passage 4l and in part through a Areturn passage 42. The gas recycled through passage 40 tends to divert the stream' ejected from orifice 36 toward passage 38, whereas the gas flowing through passage 42 tends to divert the stream toward passage 37. -The two recycle streams act in opposition to one another in such a manner that v:my y oscillati'.' as of thc main stream between passages 37 and 3S are established. The frequency of these oscillations is a I'unction of the molecular weight of the gas stream f introduced into thc oscillator. An increase in molecular weight of the gas stream tends to decrease the frequen-:y of theoscillations due to the greater inertia of the gas stream.

In one specific embodiment of this nventi'on, the apparatus of FIGUREZ was constructed in accordance vwith the dimensions (expressed in inches) `and angles set` forth in the following table:

' let passages,k diverting a portion of the fluid from the Plate 32 was formed of a sheet of metal having a thickness of approximately 0.015 inch. The passages illustrated were etched from this plate, and the plate was bonded between twoppticallyat glass plates and 31. When helium was inrodnced into passage 34 at a rate of approximately 30 cubic centimeters per minute, the oscillator established an output signal of approximately 30,000 cycles per second. The requency of this decreased l,when gaseous constituents other than `helium were added to the inlet gas. It should be evident that the frequency of oscillations established by any given oscillator in accordance with this invention will vary in accordance with the size of the oscillator and the `rare of flow of gas therethrough. However, this basic frequency decreases as the molecularweight of the gas increases.

The oscillator can be formed from various-'materials such as metal or glass. The passages can be formed by etch-v ing. photoetching. engraving or any similar method. Thin metal sheets can ocemployec and laminated to form passages of any desired thickness.

In a chromatographic analyzer, the beat frequency response can be calibrated initially by employing reference `samples of known-composition.

While thc oscillator of this invention has been described in conjunction with the analysis of the effluent from a chromatographic column, it should be evident that it is oy no means limited thereto. This oscillator can be employed to advantage to detect changes in composition of fluid streams from any source. Any change in density of fluid directed through' the oscillator will change the frequency of oscillations established. The oscillator can readily be calibrated by the use .of reference fluids of known composition. While the device ymust be calibrated in any given application, itprovides a simple device for measuring fluid compositions. When employed lto measure a single stream, the frequency of the detected vibrations can be measured directly or compared with the output signal from a reference oscillator of constant frequency. An important advantage of the oscillator of this invention is that no moving parts are employed in the oscillator itself.

While the invention has been described in conjunction with a presently preferred embodiment, it should be evident that it is not limited thereto.

What is claimed is:

l. Apparatus for use in analyzing fluids comprising means forming a fluid passage, means to direct a first stream of the fluid to be analyzed through said passage, means to divert the first stream at the outlet of said pas-, sage into second and third streams, means to return a portion kof said second stream :o said V:assage in a direction so as to tend to divert a greater portion of said first stream into said third stream, means to return a portion of said third stream to said passage in a direction so as to lend to divert a greater portion oi said first stream into said second stream, thereby establishing oscillatory fluctuations ofthe second andthird streams, a vibration derector positioned to be actuated by al least a portiorrotsecond passage and directing such divertedfluid into the first passage in a direction such as to impingeupon the` fluid flowing through the first passage and tend to divert .v

the fluid from the rst passage into the third passage, diverting a portion of the fluid from the third passage and directing such diverted fluid into the first passage in a direction such as to impinge upon the fluid flowing through the first passage and tend to divert the fluid from the first passage intotlre second passage, and measuring the frequency of vibrations established by the resulting oscillatory fluid flow, whereby changes in the measured frequency are indicative of changes in composition of the fluid stream directed through said first passage.

3. The method of detecting changes in the composition of the ellluent fluid from a chromatographic column which comprises directing such effluent fluid through a Nfirst passage, kremoving fluid from the first passage through second and third outlet passages, diverting a portion of the fluid from the second passage and directing such diverted fluid into the first passage in a direction such as to impinge upon the fluid flowing through the first passage and tend to divert the fluid from the first passage into the third passage, diverting a portion of the iluid from the-third passage and directing suchv diverted fluid into the first passar'e in a direction such as to impinge upon'is: fluid r through the first passage and tend to divert the fluid from the first passage into the second passage, and measuring the frequency of vibrations established by the resulting oscillatory fluid flow,

whereby changes in the measured frequency are indicative of changes in composition of the eflluent from the chromatographic column.

4. In a chromatographic analysis system wherein a fluid sample to be analyzed is introduced into a chromatographic column, and a carrier gas is directed through ythe column to elute the constituents of the fluid sample;

apparatus for detecting the eluted csnstituentsvcomprising first and second detectors, each comprising means forming a fluid passage, means to divert fluid at the'outlct of said passare into second and third streams, means to return a portion of :aid second stream to saidA passagel in a direction so as to tend to divert a greater portion of the fluid in said passage into said third stream, and means to return a portion of said third stream to said passage in a direction so as to tend to divert a greater portion of the fluid ir: said passage into said second stream; means to direct the effluent from the column through the fluid passage of' said first detector; ,means to direct a stream of reference carrier gas through the fluid passage of said second detectar; a first vibration sensing means positioned adjacent said first detector; a second vibration sensing means positioned adjacent said second detector; and means connected to said first and second 'apparatus for detecting the eluted constituents comprising means forming a fluid passage, means to direct the efllueat from the column through said passage as a first stream, means to divert the first stream at the outlet of said passage into second and third streams, means to rcturn a portion of said second stream to said passage in a 3,273,377 Y I s n Y A y e direction so as lo tcndtc. diver! a grenier portie of said References Cited bj' the' Examiner e l n first slrearn Inte slaid thm. siream, means'to n urn :1 por.. UNITED STATES PATENTS Y' non of said thzrd stream so said passage m a direction so as to` tend to divert a greazer porion of said rst sircam 3,144,762 8./1964 Testcrman ein! 73-23.l

into said second stream, :1 vibration detector posicned 5 3,158,166` 11/1964 Warren., v tube actuated by one of said rs and second streams,V l Y A and'meuns, ccnncced to Sad vbration detector to mea- RICHARD C. QUEISSER, Primary Examiner. sre the frequencyj-'ibraons received by ,said deector. 1, c 

4. IN A CHROMATOGRAPHIC ANALYSIS SYSTEM WHEREIN A FLUID SAMPLE TO BE ANALYZED IS INTRODUCED INTO A CHROMATOGRAPHIC COLUMN, AND A CARRIER GAS IS DIRECTED THROUGH THE COLUMN TO ELUTE THE CONSTITUENTS OF THE FLUID SAMPLE; APPARATUS FOR DETECTING THE ELUTED CONSTITUENTS COMPRISING FIRST AND SECOND DETECTORS, EACH COMPRISING MEANS FORMING A FLUID PASSAGE, MEANS TO DIVERT FLUID AT THE OUTLET OF THE SAID PASSAGE INTO SECOND AND THIRD STREAMS, MEANS TO RETURN A PORTION OF SAID SECOND STREAM TO SAID PASSAGE IN A DIRECTION SO AS TO TEND TO DIVERT A GREATER PORTION OF THE FLUID IN SAID PASSAGE INTO SAID THIRD STREAM, AND MEANS TO RETURN A PORTION OF SAID THIRD STREAM TO SAID PASSAGE IN A DIRECTION SO AS TO TEND TO DIVERT A GREATER PORTION OF THE FLUID IN SAID PASSAGE INTO SAID SECOND STREAM; MEANS TO DIRECT THE EFFLUENT FROM THE COLUMN THROUGH THE FLUID PASSAGE OF SAID FIRST DETECTOR; MEANS TO DIRECT A STREAM OF REFERENCE CARRIER GAS THROUGH THE FLUID PASSAGE OF SAID SECOND DETECTOR; A FIRST VIBRATION SENSING MEANS POSITIONED ADJACNET SAID FIRST DETECTOR; A SECOND VIBRATION SENSING MEANS POSITIONED ADJACENT SAID SECOND DETECTOR; AND MEANS CONNECTED TO SAID FIRST AND SECOND SENSING MEANS TO MEASURE THE DIFFERENCE BETWEEN THE FREQUENCIES OF THE VIBRATIONS RECEIVED BY SAID FIRST AND SECOND SENSING MEANS. 